Water-insoluble mono-azodyestuff and fiber dyed therewith



Patented Sept. 19, 1933 UNITED s'rA'nzs PATENT OFFICE:

Heinz WATER-INSOLUBLE MONO-AZODYESTUFF AND FIBER DYED THEREWITH Eichwede, Franktorton the Main Hochst, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware I No -Drawing. Application October 0 18, 1932, Serial No. 638,384, and in Germany November 13, 1931 10 Claims. (Cl. 26095) The present invention relates to water-insoluble monoazodyestufis and to fiber dyed therewith, more particularly it relates to dyestuffs cor- 5 responding to the following general formula: I

wherein R stands for a radical of the benzene series, X stands for hydrogen, halogen, an alkyl or alkoxy group and Z stands for a radical of the benzene or naphthalene series.

I have found that dyestuffs dyeing clear scarlet tobluish-red' tints are obtained by coupling a diazo-compound of a base of the general formula NHz

wherein R represents a radical of the benzene series and X represents hydrogen, halogen, an alkyl or alkoxy group, in substance, on the fiber, or on any of the usual substrata which are adapted for the production of lakes, with an arylide of the 2.3-hydroxynaphthoic acid, such dyestufi components, however, being excluded which contain groups that would render the dyestuffs solublein water'as, for instance, the sulfonic or the carboxylic acid group.

distinguished, in general, by a good iastness to light; when produced on the possess a good fastness' to soaping. The soaping test is carried out by boiling 2 grams of dye The dyestufis are fiber, moreover they material for half-an-hour with 200 cc. of water containing 1 gram of Marseilles soap and 0.6 gram of calcined sodium carbonate, cooling to 40 C. within halt-an-hour, squeezing out the I material between the balls of the hands 10 times. by dipping it into the bath, taking it out and squeezing it, and finally rinsing it in cold water and drying it.

The bases, identified by the above formula, are

obtainable, for instance, by responding nitrobenzene-su condensing the corlio-chloride with a diphenylamine and reducing the condensation product thus obtained. 1 The properties of some 0 follows:

i these bases are as Melting point 1 aminobenzene-5-sulfodiphenylamide-colorless crystalsQ 102 C.

1 amino 2-methylbenzene-5- sulfodiphenylamide colorless crystals 1 amino-2-methoxybenzene-5- sulfodiphenylamide colorless crystals 1 amino 2-chlorobenzene 5- sulfodiphenylamide colorless crystals 133 C. to 135 C.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto:

Dyeing prescriptions for'the Examples 1 and 2 grams of well boiled cotton yarn are impregnated for half-an-hour with the grounding liquor, squeezed or hydroextracted and dyed for half-an-hour in the dye-bath. Thereupon, the dyed yarn is well rinsed, soaped'at the boil with 2 grams of Marseilles soap and 1 gram of sodium carbonate per liter, rinsed and dried.

(1) a. Grounding liquor 129 C. to 130 C.

5 grams of 1(2'3'-hydroxynaphthoylamino) 2-methoxybenzene are dissolved in boiling water in known manner with 10 of'Turkey red oil of 50 per cent.

. strength and 7.5 cc. of caustic soda solution of 34 B.;

after coolingto 50 C. 1 cc. of formaldehyde of 33 per cent.

5 I strength are added and the whole v is made up with water to b. Dye-bath 3.59 grams of 1-amino-2-methoxybenzene-5- sulfodiphenylamide are 'diaz'otized with l middle red ofgood fastness to light, towashing and to chlorine is obtained.

149 C. to 152 C.

The dyestuif has the following formula:

HaCO

(2) a. Grounding liquor;

OCH:

6 grams of 1(23'-hydroxynaphthoy1amino)- d-methoxybenzene are dissolved in boiling water inknown manner with l by weight of sodium nitrite.

pound is run into a :finely dispersed suspension of A yellowish red of good fastness to light, to washing and to chlorine is obtained.

The dyestuff has the following formula o O-NHOOGHa (3) 35.9 parts by weight of 1-aminobenzene-5- sulfodiphenylarnide are diazotized in usual manner in a hydrochloric acid'solution with 7 parts The diazo-com- 26.3 parts of 2.3-hydroXynaphthoyl-aminobenzene; By slowly adding, drop by drop, a solution of sodium acetate or sodium carbonate, the free mineral acid is rendered'neutral. After .the coupling is-finished, the dyestuff is filtered by suction, washed'for a short time and dried. It

- b. Dye-bath 3.39 grams of 1-amino-2 1nethylbenzene-5- sulfodiphenylamide are diazotized with forms a scarlet-red powder.

The dyestuff has the following formula:

NZN

cc. of hydrochloric acid of 20.B. and V 8 o u g 1r1te.1 10. r The following table indicates a number of other l, 10 f g? a 1 g d combinations obtainable according to the present 110 25 grams so f g e e h 1 process but does not comprise all possibilities for grams sodmm g 5 w 0 e 15 the preparation of dyestuffs by using different m 5 u W1 er 0 components; it, therefore, is not intended to limit the invention to the dyestuffs mentioned 1000 cc. therein.

Diazotizing component Coupling component Tint (l) i-amine-2-methoxybenzene-S-sulfodiphenylamide 1(2'3-hydroxynaphthovlamino)-4-motlioxybenzene Middle red (2) l-amino-l-methoxybenzene 5-suliodiphenvlarnido l(23-hydroxynaphthoylamino)-naphthalene Middle red (3) 1-an1ino-2-rnethoxybenzene-S sulfodiphenylamide: 2(23'-hydroxynaphthoylamino)-naphtlialene:I:. .Bluish-red (4) 1am no2-methoxybonzone-Ssul(od phenylam de 1(2:3Zhydroxynnphtlmylamino)-2-Inethyl-4ch10robe Vivid bluish-red $3 1'22?38'5312318153fifiiifii'i'ifiii$32333253 531?ti itt i t a zii ii ii ,1 ox mi 110 n. e s- (7) l-amino-iZ-methoxybenzeno 5-suliodiphenylamide 1(23 hydr 5yiaphmlinin$ i iethylben. Mid l e red (8) 1-a1n1no-Z-methoxybenzene-fi-sulfodiphenylannde. l(%3-hydroxynaphthoylamino)-2.4-dimethoxy Vividyellowish-red enzone p h (9) 1-ammo2-mcthoxybenzene5suli0d1phenylamidel(%3-hydroxynaphthoylamino)-2.5-dimethoxy4-chloro- Yellowish-red I enzene 4 V (10) 1-amino-2 methoxybenzene-Lj-sulfodiphenylamide. l(23 -hydroxynaphthoylamino)-2ethoxybenzene Scarlet (ll) 1-amino-2rmethoxybenzene-a-sulfodiplicnylamide. 1(2)3-hydroxynaphthoylamino)-2.4-dimethoxy-5-chloro- Bluisli-red 8117,9118. v I (l2) l-am no-2-methmrybenzene-S-sullod phenylam de l(2i3i-hydroxynaphthoylamino)-2-methyl-5-chlorobenzene. Vivid bluish-red (3) -am no-2-methmybonzene-5-sulfod phenylam de 1(23 -hydroxynaphthoylam no)4-1nethylbenzene..- V v d yellow sh-red (14) l-armno-2-methoxybenzene-5-sulfodiphenylamide 1(23 -hydroxynaphthoylammo -2-Inethoxy-5-chl0roben- Vivid yellowish-red z (lg) i-mn nog-metliloxygenzene-S-sulfodrphenylam de l(2:Eli-hydroxynaphthoylamino)-4-chlprobenzene Vividyellowish-red' (17) -am nonet oxy enzene-S-sulfod phenylam de l(2 3 -hydroxynaphthoylnm no)-2.5- limethoxybenzene;l Yellowish-red 1-am1no-. -n1ethoxybenzone-fi-suliodiplienylannde 1(2 3 -hydroxynaphthoylammo) 2-metl1yl-4-niethoxyben- Bluish-rcd I zone. Y v 833 iIifiifi tlfiiigitZ35fii i ifiififi tifi iifiifii iE3 i %"fi tifi i 'iii Vividswl 20 1-amino-2-methylbeniene-5-sulfodighengrlamide:I: 2 2c ihtdigitfiifimhitifiififii fiifihthiiifiiitjjj I Y e l l vffs li r gd, (3%) l-amrno-Q-rnethylbenzene--sulfodrphenylamrde. l(2C3L-hydroxynaphthoylaminc)-2-methyM-chl0robenzene. Vivid scarlet -am1 no-2 methylbenzenc-c-sulfodrphenylamrdc. 1(23-hydroxynaphthoylamino)-2-methylbcnzene VlVld scarlet (23) l-ammo-Z-methylbenzene-fi-sulfod1phenylam1de. l(23-hydr0xynaphthoylam1110)-2-methoxy-4-chloroben-. Scarlet H zcne. (24) 1-amino-2-methylbenzene-5-sulfodiphenylamide. 2.3-hydroxynaphthoylaminabenzene Vivid scarlet (25) 1-am1no-2-methylbenzene-E-sulfodiphenylamide. 1(23-hydroxvnaphthoylamino)-3-nitrobenzene Vivid carlet (26) l-amino-Zniethylbcnzene-fi-suliodiphenylamide l(23-hydroxynaphthoylamino)-4-chlorobenzene Vivid carlet (27) l-amino-2 mcthylbenzene-5-su1fodiphenylamidc I l(23-hydrovvnaphthovlsirnirio)- -mcthy1henzene Vivid carlet (28) l-amino-2-Inethylbenzene-5-sul[odiphenylamide:l 1(23-hydroi ynaphthoy1amino)-2-ethoxybenzonet.. Vivid scarlet" g3) i-am no-2-methylbenzene-5-suliod phenylam delEZLSZ-hydroxynaphthoylarnino)-2-methyl-'3-chlorobenzene. Vivid scarlet -am1no-2-methylhenzene-5-suliodiplienylamide. 1 %)3-hydIOXYI1ElPhthOY1llB1lIlO)'2.fi-dllIlGthOXY-3-Clll0f0' Vivid scarlet I enzene- 7 (31) 1-amino-2-Inethy1benzene-5-sulfod1phenylam1de l(23 hydroxynaphthoylaminc)-2-methy1-4-methoxybon- YelloWish-red zene I (32) 1-amino-2-methy1benzene-5-su1fodlphonyla nida. l(gy-hydroxynaphthoylamino)2.4-dimethoxy 5-ch1or0 Middle red enzene V l l-amrn0%enzene-fi-sulfod phenylam de 1(2:3:-hydroxynaphthoylamino)-2-inethyl-4-chlorobenzene Scarlet -al nmo engene-snlfodiphenylamlde 1(23-hydroxynaphthoylannno)-2-Inethoxyl-chloroben Scarlet V y u I zene y (35) l-umlnobenzene-fi-suliod phenylarnide... 1(2'3-hydroxynaphthoylamino)-2-metl1oxybenzene Scarlet- Since an object of the present invention is to provide dyestuffs of good fastness properties, which dyestuffs are insoluble in Water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to deprered shades and being distinguished by their good fastness properties.

3. The water-insoluble mono-azodyestufi of the following formula:

dyeing a bluish-red shade and being distinguished by its good fastness properties.

4. The water-insoluble mono-azodyestuff of the following formula:

Q 0113 OH H1O? ciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

I claim:

1. The water-insoluble mono-azodyestuffs of the following general formula:

wherein R stands for a radical of the benzene series, X stands for hydrogen, halogen, an alkyl or alkoxy group and Z stands for a radical of the benzene or naphthalene series, dyeing clear scarlet to bluishwred shades and being distinguished by their good fastness properties.

2. The water-insoluble mono-azodyestuffs of the following general formula wherein X stands for a methyl or methoxy group and Z stands for a radical of the benzene or naphthalene series, dyeing clear scarlet to bluishdyeing a vivid scarlet shade and being distinguished by its good fastness properties.

5. The water-insoluble mono-azodyestuff of the following formula: 

